Anthraquinonyl-triazine or -pyrimidine dyestuffs



United States Patent 3,496,174 ANTHRAQUINONYL-TRIAZINE 0R -PYRIMIDINEDYESTUFFS Dennis Eckersley and Robert Norman Heslop, Manchester,England, assignors to Imperial Chemical Industries Limited, London,England, a corporation of Great Britain No Drawing. Filed Nov. 13, 1967,Ser. No. 682,505 Claims priority, application Great Britain, Nov. 29,1966, 53,435/ 66 Int. Cl. C07d 55/48, 51/42 US. Cl. 260-249 4 ClaimsABSTRACT OF THE DISCLOSURE The reaction products of cyanuric chloride,2,4,5,6- tetrachloropyrimidine, 5 cyano-2,4,6-trichloropyrimidine or theanalogous bromo compounds with (1) a l-amino- 2-sulpho-4-(aminoanilino)anthraquinone in which the 2,6 positions of the anilino radical aresubstituted with alkyl or halogen and (2) an aniline or naphthylaminecontaining an alkyl sulphamyl group in which alkyl group contains a C1or Br atom or sulphato group in the 18 position or Cl, Br or OH in the 5position together with C1 or Br in the 1 position; these products arevery bright reddish-blue cellulose-reactive dyes having a very highpercentage fixation on the fibre.

, This invention relates to new water-soluble reactive anthraquinonedyestufis, to the methods of preparation thereof and to the use of suchdyestuffs for colouring textile materials.

It is known to use dyestuffs containing halogeno-s-triazine or halogenopyrimidine groups for the purpose of colouring fibres containinghydroxyl groups, especially cellulose materials such as cotton andviscose rayon.

These dyestuffs readily fix on such materials with good fastness to wetprocessing, since the halogen atom on the s-triazine or pyrimidinenucleus is able to react with hydroxyl groups of the cellulose moleculein the presence of acid-binding agents, especially at elevatedtemperatures. For this purpose, the dyestuffs are applied from aqueoussolution or aqueous printing pastes and, owing to a sidereaction inwhich the halogen atom reacts with water instead of the cellulosemolecule, a considerable portion of the dyestufi does not fix on thefibre.

Consequently an excess of dyestutf must be used and the dyeings orprints must be thoroughly washed with boiling soap solutions to removethe unfixed dyestuff. The wastage of dyestutf and extra processing makethe dyeing or printing process more expensive especially when deepshades are required.

The present invention is concerned with the production of water-solublehalogeno-s-triazine and halogeno pyrimidine reactive dyestuffs whichhave a remarkably high fixation on the fibre and for which washing-offtreatments can be reduced considerably.

According to the invention there are provided reactive water-solubleanthraquinone dyestuffs of the formula:

"ice

wherein Z and Z each independently represents H or SO H;

R is methyl or ethyl,

R represents a chlorine or bromine atom or methyl or ethyl group,

R represents a hydrogen atom or a methyl or ethyl group,

Y represents C1 or Br;

X represents N, C-Cl or CC-N,

R represents a hydrogen or an alkyl group having up to 4 carbon atoms,

A represents a phenylene or naphthylene radical in which the nucleus cancarry one or more substituents,

B represents S0 or CO and R represents an alkyl group of at least 2carbon atoms, having a Cl, Br or OSO H substituent in the fi-position orhaving both a Cl, Br or OH substituent in the fi-position and a Cl or Brsubstituent in the 7 position.

In the above formula, Z preferably represents hydrogen; R, R and Rpreferably each represents a methyl group, R can be ortho, meta or parato R. Z preferably represents SO H, R preferably represents hydrogen, Apreferably represents a phenylene or naphthylene radical carrying asecond B NHR radical, B preferably represents S0 and R preferablyrepresents an alkyl radical, substituted as stated, having at most 3carbon atoms, above all, a B-sulphato ethyl or ,B-sulphatopropylradical.

According to a further feature of the invention there is provided aprocess for manufacture of the new anthraquinone dyestuffs whichcomprises condensing a heterocyclic compound of the formula:

wherein X and Y have the meanings stated above, in

either order, with (a) one molecular proportion of anamino-anthraquinone compound of the formula:

0 NH2 H SO3H NH2 R Z (3) wherein R R R Z and Z have the meanings statedabove and (b) one molecular proportion of an amine of the formula:

wherein A B R and R have the meanings stated above. As examples ofcompounds of Formula 2 there may be mentioned cyanuric chloride,cyanuric bromide, 2,4, 5,6-tetrach1oroand tetra-bromopyrimidine,5-nitro-2,4,6- trichloroand tribromopyrimidines and5-cyano-2,4,6-trichloroand tribromo-pyrimidines.

As examples of compounds of formula (3) there may minutes to a stirredsuspension of 3.75 parts of cyanuric chloride in 20 parts of acetone and15 parts of water at -5 C. The pH of the mixture is maintained at4.5-5.0 by the addition, when necesarry of 2 N sodium carbonate andstirring under these conditions is continued for a be mentioned1-amino-4-(3'-amino-2'4',6'-trimethylani- 5 further 1 hour. The reactionmixture is then filtered, the lino)anthraquinone-2,5-disulphonic acid,1-amino-4(4- filtrates to "pH 6.4 and a neutral solution of 12.4 partsof amino 2',3',6' trimethylanilino)anthraquinone-2,5-dithe disodium saltof 4,8-bis-(fl-sulphatopropylsulphamyl) sulphonic acid,1-a'rnino-4(4-amino-2',6-dimethyl or dinaphthyl-Z-amine in 190 parts ofwater is added. The ethyl anilino)anthraquinone-Z,5-disulphonic acids,1- mixture is stirred at 35-40" C. and at pH 6.5-7.0 for 2amino-4(4-amino-2' methyl 6' chloroanil'ino)anthrahours, a further 1.55parts of the above fi-sulphatoproquinone-Z-sulphonic acid. pylsulpharnylcompound dissolved in 25 pa-rts of water is As examples of amine offormula (4) there may be added and stirring at 43-45 C. and pH 6.5-7.0continued mentioned 4-(flchloroethylsulphamyl)aniline, 3(B-chlofor 8hours. The reaction mixture is filtered, the solutionroethylsulphamyl)-aniline, 3,5-di(ii-chloroethylsulphamtreated with 30%(W./w.) sodium chloride with stirring yl)aniline, 3- or4-({i-sulphatoethylsulphamyl)aniline, 4- and the precipitated dyestufffiltered and washed with (v chloro-fl-hydroxypropylsulphamyl)aniline,4-(fi,'y 30% (w./v.) sodium chloride solution. The product isdichloropropylsulphamyl)aniline, 4-(5 chloropropylsulpurified byredissolving in water and reprecipitating phamyl)anil*ine,4-('y-bromo-B-hydroxypropylsulphamyl) from its solution by the gradualaddition of 34% (w./v.) aniline,Z-methoxy-S-('y-chloro-fi-hydroxypropylsulphamsodium chloride; it isfinally isolated by filtration, washing yl)aniline,6-(fl-chloroethylsulphamyl)-2-naphthylamine, with 26% (w./v.) sodiumchloride solution and drying. 3-(fl-chloroorB-sulphatoethylsulphamyl)aniline, Z-me- The product dyes cellulosictextile material in bright thoxy-S-(B-chloroorB-sulphatoethylsulphamyl)aniline, reddish-blue shades of excellentfastness to Wet treatments 4-(ti-sulphatoethylcarbamyl)aniline,B-(fi-chloroethylcarand to light. carbarnyl)aniline and4-(fl-sulphatopropylsulphamyl)-N- methylaniline. EXAMPLE 2 The aboveprocess can conveniently be carried out by suspending or.dissolving theheierocyclic conipqund in A neutral solution of 11.5 parts of thedisodium salt water or a mixture of water with a water-miscible or- 30 1amino 4 (3, amino 2,,4,,6 trimethylanilino) anthra game p adduig of theother .reagents 9 quinone-2,5-disulphonic acid in 300 parts of water isa solutlonfihiereof m Water or a watqr'mlsclble Orgamc added during 25minutes to a stirred suspension of 4.59 f Surfing. the mlxtuie at asultable temperamlie parts of 5 cyano-2,4,6 trichloropy-rimidine in 50parts of 1mm one chlorme or bromine g i i i a dioxan and 100 parts ofwater at 10-15" C. The pH of ?ompound.has been reacted f Stamlal en athe mixture is maintained at 4.5-5 .0 by the addition of mg the thudreaataint and stlmng sliltab i 2 N sodium carbonate and stirring underthese conditions ature to efiect reaction of the second 6 i i i iscontinued for a further 1 hour. The reacion mixture is atom In general atempgramre of 0 2 2 then filtered, the filtrates adjusted to pH 6 .5 anda neutral the first Step and a temperature 0 18 solution of 7.5 parts of4-(fl-sulphatopropylsulphamyl) suitable for the second step. Thereaction lS preferably 100 f dd h carried out in the presence of anacid-binding agent, 40 me m Karts 0 Water Is 3 T e mixtum.ls added atsuch a rate as to maintain the pH of the reaction Stirmd at 55*60 for 6hours whilst f PH 13 mixture between the limits of 4 and 8. tamed at pH6.0-6.5 by the gradual add tion of 2N so- The new dyestuffs wn beisolated by any of the usual drum carbonate solution. 100 parts ofsodium ChlOPldC are means usfid in Connection with water solublereactive added and the mixture is allowed to stir and cool for 2dyestuffs, preferably by the addition of sodium chloride, hOIlYS- ThePrecipitated y ufi is fi tered Washed on the and filtering olf theprecipitated dyestulf and drying. filter with 300 parts of 25%, W./v.)sodium chloride solu- The new dyestuffs can be used for dyeing orprinting tion, sucked dry and is finally dr-ied in vacuo at 20 C. a widevariety of textile materials. They are particularly The product wasfound on analysis to contain 1 atom valuable for use as reactive dyesfor cellulose with which of hydrolysajble hl i d 3 atoms f l h y are(32113931316, 11716 Pfiisence 0f fifcid-ibilldiffg ageflts, 5O moleculeof dyestufl and when applied to cellulosic texof reacting Wlth a highdegree of efiiclency to bright tile materials in conjunction with anacid-binding agent r lf fi' shades of excellent fasmess to washmg andyielded strong-bright reddish blue tints of excellent fast- 0 1g ness toWet treatments and 1i ht.

I invention. ilhistmted but not limited by the The following table givesfurther examples of the new lowing example m Whlch parts by Welght'dyestuffs of the invention which can be obtained by the method ofExample 1 by condensing the sodium salts of EXAMPLE 1 the anthraquinonecompounds listed in column 1 with an equivalent proportion of theheterocyclic compounds A neutral solution of 8.85 parts of 1-amino-4-(3-listed in columnZ and reacting the compound so obtained amino 2,4,6trimethylanilino)anthraquinone-2-5'-diwith an equivalent PIOPOIHQII 0fthe amiflfi listed n sulphonic acid in 250 parts of water is addedduring 15 column 3.

Heterocyclie Example Anthraquinone compounds compound Amine 3LaminoA-(S'amino-Z'A,6'-trimethylanilino) anthraquinone- Cyanurlcchloride..- 4(B-chloroethylsulphamyl)-N metllylanilins.

2,5-disulphonic acid. I 4 1-aminc-4-(4-amino-2,3',6'-trhnethylanilino)anthraqulnonedo 4(Bsulphatoethylcarbamyl)-an1lme.

2,5'-disulphonic acid. I 5 do .do 4(7-0111010fl-hydroxypropylsulphamyl)-amlme. 61-amino-4-(3-amino-2',4',6-triethylanilino)anthraquinone- .d0 3,5bis(6-sulpl1atopropylsulphamyl)-aniline.

2,5' disulphonie acid. 4 7 do d0 8-ammo-5(Bchloroethylsulphamyl)-benzo1cacid 8 1-amino4-(3'-amino-2,4,6'-trimethylani1ino)anthraquinone-Cyanuric bromide..." 3,5 bis(fi-sulphatoethylsulphamyl)-aniline.

What we claim is:

the formula:

wherein Z and Z each independently represents H or SO H;

R is methyl or ethyl R represents a hydrogen atom or a methyl or ethylor ethyl group R represents a hydrogen atom or a methyl or ethyl p:

Y represents C1 or Br;

X represents N, CCl or CCN,

R represents a hydrogen atom or an alkyl group having up to 4 carbonatoms,

A represents a phenylene or naphthylene radical in which the nucleus cancarry one or more substituents selected from the group consisting ofphenylene, naphthylene, carboxyphenylene, phenylene containing a second-B'NHR group and naphthylene containing a second BNHR group,

B represents S0 or CO and R represents an alkyl group of 2 or 3 carbonatoms, having a Cl, Br or OSO I-I substituent in the fi-position orhaving both a Cl, Br or OH substituent in the fi-position and a C1 or Brsubstituent in the 'y position.

2. A dyestutf as claimed in claim 1 and represented by the formula:

f) NHz SO=H CH; S|OzNHCHzO1lOH so H NH -NH-o pNH a 1G CHa- CH: \C/

SO; (11 SO2NHCH2CH.CH:

References Cited UNITED STATES PATENTS 3,133,921 5/1964 Brassel et al260249 3,397,207 8/1968 Barben et a1. 260249 3,427,308 2/ 1969 Barben eta1. 260249 XR HENRY R. JILES, Primary Examiner I. M. FORD, AssistantExaminer US. Cl. X.R.

